Esters of product obtained by reacting pentaerythritol and thiodiglycol



Patented July 12, 1949 UNITED STATES PATENT OFFICE 2.478.129 ESTEBS 0F PRODUCT OBT INED BY REACT- ING Fredrick B. Augustine, Jefferson,

PENTAERYTHRITOL AND 538101)!- to Smelly-Vacuum Oil Company, Incorporated. a corporation of New York No Drawing. Application July 3, 1047,

10 Claims. (0]. 280-399) This invention relates to esters of reaction products formed by the interaction of pentaas plasticizers, coating compositions, resins, drying oils. synthetic improving agents. 7 Esters oi pentaerythrltol and polypentaerythrito! are well known and are assumin increasing 10 an etheriflcation those mentioned by Burrell.

The pentaerythritol-thiodiglycol products of 1 as compared with pentaerythrito] and polypentaerythritol.

REACTANTs Pentaerythrltol primary reactant in the process of this invenprocess or this invention, or tri-pentaerythritols in mixtures probably contains dilesser amounts, such part of this invention. 1 may be used if desired. indicated that dipentamay and often other compounds, such for example as dithlodiglycol.

The preferred secondary reactant,

comprised, at least principally, oi monothiodiglycol.

The esteriflcation reagent may be any monocarboxylic acid, anhydride or acid chloride.

an amount equal to 10% thiodiglycol and this catalyst in pears to be vary satisfactory.

The use of a catalyst does not appear to be necessary in the REACTION CONDITIONS The ratio of pentaerythritol, the primary reactant, to thiodlglycol. the second reactant, should be between about 0.3 and 0.9 moi oi thiodigiycol per mol of pentaerythrltol. Ratios oi less than 0.5 presumably leave some pentaerythritol unreacted but the products are nevertheless of considerable value. with ratios lower than about 0.5, the weight per cent of thiodiglycol is too low to aflord suillcient solvent power necessary to make the reaction easy to accomplish. with ratios approaching l and higher more or less soluble gels and high molecular weight condensation products are obtained, which esterify only with difllculty, ii at all, and which are apt to break down into smaller units. This difficulty began to be evident. experimentally, of 0.9.

In the esterification reaction it has, generally, been found desirable to have an excess oi the esterirying reactant present over the amount that will react with the condensation product, but no very great excess appears be necessary. fact, it there is any danger that the pentaerythritolhlodiglycoi products may break down into smaller units, it is preierable not to have any great excess the esteriilcation reactant present, for such excess may tend to promote this cracking reaction. i 'rom one-half to three amount of esteriiication agent that will react, may be present. Amounts outside of these limits appear impractical irom a commercial standint.

in reacting the pentaerythritol with thlodi glycol it is preferable to min the pentaerythritol and thiodiglycol and raise the temperature of the mixture until an appreciable amount of the pentaerythritol dissolves in the thiodlglycol before adding the catalyst. Experimentally, the temperature necessary to accomplish this dispehtaerythrltol in the thiodigiycol to be about 145 C. to 175 C.

been found satisfactory for the continuation of the reaction between the pentaerythritol and the thiodiglycol as well as for the subsequent esterliication. However, in more diflicult esteriflcations, as with the higher fatty acids, higher reaction temperatures, even as high as about 250 C. may be advantageous.

Because water is a lay-product oi both of the reactions, provision i'or the removal of water favors these reactions. The water may be allowed simply to distill out or, preferably, it may be carried out in a stream oi. inert gas. The use of a solvent or inert reaction medium which will absorb the water, and from which the water can be separated before reuse, is desirable especially when higher reaction temperatures are undesirable or when a water-soluble, low-boiling esteriilcation reactant is employed.

The time necessary for the reaction between the thiodiglycol and pentaerythritol is best estiat d by the amount or water evolved as is also the amount of time necessary for the esterificathe presence tion will be apparent irom the ll by heating was s.

m was introduced.

a were added, and

' washed once with hu'ther in Table 1.

times the m tion reaction. Usually, 0.5 to 1 hour is suflicient tor the first reaction and 1.5 to 3 hours for the second.

Further details and advantages oi this inveniollowing specific In these examples a commercially available pentaerythrltol 0! technical grade mel ing at about 235 C. was used. A technical grade 0! thiodiglycol was also used.

One-r: or PIMAIRYTHRI'I'OL-THIODIGLYOOL Psonnc'r To the slurry or incomplete solution obtained or thiodiglycol (0.6 moi) and 109 g. of pentaerythritol (0.8 mol) to 145 C. was added '1 g. of p-toluene sulphonlc acid monohydrate. Immediately, a clear solution resulted and water distilled out in the stream 0! nitrogen which lated amount oi water. 21.5 ec., had been collected. At this stage the polymeric product was a very viscous liquid, almost a gel. However, it was dissolved when 564 g. of oleic acid (2 mole) esteriflcation took place at 165 C. as was evidenced by the distillation 0! water. A total oi 30.5 cc. was collected in a reaction time or minutes.

The crude product was dissolved in benzene,

aqueous sodium carbonate solutlon and three times with water, and topped under vacuum, finally to 160 C. pot temperature at 4 The residue, 818 g. or 90% of calculated yield, was a viscous oil. it is described EXAIEPL II Burma-rs or Pmsramsrrot-Tmonrotycor. Pnonnc'r 5 tion resulted and water was evolved rapidly until a total of 1'! cc. had been collected.

To 60 g. of this polymeric product (Ye of a calculated moi) were added 103 g. of butyric acid (l /6 mols). A clear solution was obtained at 110 C. No catalyst was added although some final reaction at toluene sulphonlc acid may have remained after the etheriflcation reaction. As the temperature was raised to 0. water and some butyrlc acid distilled in the stream or nitrogen provided. After 145-155 C. for 50 minutes, the water content of the distillate was estimated to be 16 cc.

The reaction product, without further treatment. was topped to C. pot temperature at 0.5 mm. pressure. A yield oi 12'? g.. 97.5% of theoretical based on the intermediate polymer, was obtained as a water-white. neutral oil. tional properties of this product are given in Table I.

EXAMPL III BU'L'YRATIB or OTHER musty-manor.-

Tinomct'rcoi. Plion'oc'rs Withln 20 minutes the calcupentaerythritol and technical polypentaerythri, acids, and acid chlorides of aliphatic monocart boxylic acids, at a temperature falling within the In Table II the use of the oleate of Example I range varying between about 145 C. and about as an additive for improving the viscosity index 250 C. of an S. A. E. grade lubricating oil is illus- 5 2. A process which comprises reacting thioditrated. It will be observed that improvement in glycol with pentaerythritol, in a ratio of between the viscosity-temperature relationship results about 0.3 mol and about 0.9 mol of thiodiglycol even at the lower concentrations. per mol of pentaerythritol, at a temperature fall- Table I PROPERTIES OF Es'rERs OF Mmnrmn PENTAERY'IHRI'IOL Sulphur Rcactant Moi Rat Saponiilcatlon K. V. Centi- No. stokes lo Examlo Type Ester Ab'IM P mr, 0 Thiod, Pentu u Slope F.

glycol Found Caicd. Found 1%), g

Percenl Parnell! I Oleete 3 2.8 3.0 1% 1 58 175.3 23.16 II Butyrflte l i 4 3 430 4.51 72.8 9.74 5(; iii

5 u :2 12:: a? 0.. I. v- I 54 III"... Butyrate ofPentaerythritoL i 538 542 19 172 g I III. Butyrate ofDipcntaerythritol l 4% 495 121.7 13,35 1 i 454 Ill liuittyraie of Polypentaerythi I 503 157.9 16.4 11:; e

Acidity expressed as mg. KOH equivalent to l g. ester.

Table II PROPERTIES OF OIL BLENDS 0F OLEATE 0F MODIFIED PENTAERYTHRITOL c F M K. V. {Dumb onc. r stoes Base on uctoi v. I. M H g" Example I De Per cent 0 35. 74 5. 69 108. 5 739 5 5 37.96 6.03 "3.5 .729 0 SAE 10 grade Oil 10 40. 56 6. (3 118. 713 5 I an 54.72 8.30 126 .671 5 100 175. 3 23.16 133.5 .541 I5 The A. S. T. M. slope and the viscosity index ing within the range varying between about 145 both express the susceptibility of an oil to change C. and about 175 C.. and in the presence of an in viscosity with change in temperature. The 45 acid catalyst. to produce a reaction product; and A. S. T. M. slope is the geometrical slope of the esterifying said reaction product with an allstraight line which results from the plotting of phatic monocarboxylic acid, at a temperature viscosity-temperature data on a standard A. S. falling within the range varying between about T. M. chart. It is most precisely obtained 145 C. and about 175 C. through use of the equation: 3. A process which comprises reacting thiodiu glycol with pentaerythritol, in a ratio of between slope [log log i q z't?'ggz about 0.3 mol and about 0.9 mol of thiodiglycol per mole of pentaerythritol, at a temperature The lower the numerical value of the slope the falling within t range varying between about more nearfy horizontal is the line and the less 55 145 Q and about 75 C and m t presence of susceptible is the oil to change in viscosity with an acid oatalyst to produce a reaction t; ge in temperature- The Viscosity index is and esterifying said reaction product with an allmore familiar but less reliable system of rating. phatic monocarboxyuc acid containing between For two oils of widely diflering viscosities, the oil about 2 carbon atoms and about 13 carbon atoms of Po Viscosity-temperature relationship may per molecule, at a temperature falling within the actually have the higher (better) viscosity index. range varying between about 45 c, and b t Such an anomaly is illustrated in lines 2 and 4 of 75 c Table I, where the true comparative rating is in- A process which comprises reacting t t dlc ed y the slopesglycol with pentaerythritol, in a ratio of between What 15 0181111911151 about 0.3 mol and about 0.9 mol of thiodiglycol 1. The p e s which comprises reacting thioper mol of pentaerythritol, at a temperature falldlglycol with pentaerythritol, in a ratio of being within the range varying between about 145 tween about 0.3 mol and about 0.9 mol of thiodi- C. and about 175 C.. and in the presence of pglycol per mol of pentaerythritoi, at a, temperatoluene sulfonic acid monohydrate, to produce a ture falling within the range varying between reaction product; and esterifying said reaction about C. and about 250 C., and in the presproduct with butyric acid, at a temperature fallence of an acid catalyst, to produce a reaction ing within the range varying between about 145 product; and esterifying said reaction product 0. and about C.

with an esteriflcation reagent selected from the 5. A process which comprises reacting thiogroup consisting of aliphatic monocarboxylic 75 diglycol. with pentaerythritol, in a ratio of beacids, anhydrides of aliphatic monocarboxylic tween about 0.3 mol and about 0.9 mol of thiodiglycol per mol pentaerythritoi. at a temperature falling within the range varying between about 145' C. and about 175 0., and in the presence o! p-toluene sulionic acid monohydrate, to produce a reaction product: and esterifying said reaction product with oleic acid, at a temperature falling within the range varying between about 146 C. and about 175' C.

6. As a new composition or matter, the prodnot obtained by reacting thiodigiycol with pentaerythritol, in a ratio or between about 0.3 mol and about 0.9 mol 0! thiodiglycol per mol of pentaerythritoi. at a temperature falling within the range varying between about 145" C. and about 250 C., and in the presence or an acid catalyst. to produce a reaction product; and esteriiying said reaction product with an esteriiication reagent selected from the group consisting of aliphatic monocarboxyiic acids, anhydrides of aliphatic monocarboxyiic acids, and acid chlorides of aliphatic monooarboxylic acids. at a temperature falling within the range varying between about 145 C. and about 250 C.

7. As a new composition of matter, the product obtained by reacting thiodiglycol with pentaerythritoi, in a ratio or between about 0.3 mol and about 0.9 mol of thiodigiycol per mol of pentaerythrltol, at a temperature falling within the range varying between about 145 C. and about 175 C., and in the presence of an acid catalyst, to produce a reaction product; and esterifying said reaction product with an aliphatic monocarboxyiic acid, at a temperature tailing within the range varying between about 145 C. and about 175 C.

8. As a new composition of matter. the product obtained by reacting thiodigiycol with pentaerythritoi, in a ratio 01 between about 0.3 mol and about 0.9 moi oi thiodigiycol per moi of pentaerythritoi, at a temperature falling within the range varying between about C. and about C., and in the "presence of an acid cataiyst. to produce a reaction product; and esterliying said reaction product with an aliphatic monocarboxylic acid containing between about 2 carbon atoms and about 18 carbon atoms per molecule, at a temperature i'ailing within the range varying between about 145 C. and about 175 C.

9. As a new composition of matter, the product obtained by reacting thiodiglycoi with pentaerythritoi, in a ratio oi between about 0.3 moi and about 0.9 mol 0! thiodigiycol per mol of pentaerythritoi, at a temperature falling within the range varying between about 145 C. and about 175 C., and in the presence of p-toluene sulionic acid, to produce a reaction product; and esteriiying said reaction product with butyric acid, at a temperature falling within the range varying between about 145" C. and about 175 C.

10. As a new composition of matter, the product obtained by reacting thiodigiycol with pentaerythritoi in a ratio of between about 0.3 mol and about 0.9 mol of thiodigiycol per mol of pentaerythritol, at a temperature falling within the range varying between about 145 C. and about 175 C., and in the presence or p-toluene sulfonic acid monohydrate. to produce a reaction product; and esteriiyinl; said reaction product with oleic acid, at a temperature falling within the range varying between about 145 C. and about 1'15" 0.

FREDERICK B. AUGUSTINE.

No references cited. 

